Treatment of sulphur bearing ores



July 30, 1935- HEcHENBLElKNER TREATMENT OF SULPHUR BEARING ORES Filed Oct. 4, 1932 KOP/Regnum A NJOOU Patented July 30, 1935 UNITED STATES PATENT OFFICE 2,009,133 v TREATMENT or sULrnUa ammo.' oars Application October 4, 1932, Serial No. 836,142

5 Claims. (Cl. 75-60) This invention relates to an improved method of treating sulphur bearing ores to desulphurize the same and to produce therefrom sulphur dioxide gas and an oxide of the metal of the ore.

5 Prime desiderata. in the desulphurizing and roasting of sulphur bearing ores such as pyrites, pyrhotite, zinc concentrates and the like are the production of a sulphur dioxide gas of high concentration suitable, for example, for the ecol nomical production of sulphuric acid or for the making of calcium bisulphite for the sulphite wood pulp industry, and the production of a socalled dead roasted ore consisting of a metal oxide suitable for direct use in smelting operations of blast furnaces and iron and steel producers. Many methods have heretofore been devised and suggested for accomplishing one or the other or even both of these desired results; and to solve the numerous difficulties involved, it has heretofore been proposed in different methods to roast the ore with carbon or hydrocarbons added thereto, to control the supply and strength of oxygen (either in the form of air or in a more concentrated form) in the roasting step, and to dilute the oxygen (air) with non-oxidizing gases such as the sulphur dioxide obtained in the process, these methods being carried out in various types of furnaces, such as the Wedge and Herreshoi furnaces and also furnaces of the rotary kiln type.

In spite of the numerous suggestions made and the many methods devised, it has not heretofore been found possible or practicable, so far as I am aware, to regulate or control the roasting reactions in the furnace to produce in any simple and economical way a sulphur dioxidegas of high concentration on the one hand and a dead roasted ore consisting of a metal oxide having a very low sulphur content on the other hand, which latter may, if desired, be properly sintered or nodulized in the roasting process without interfering with the roasting reactions taking place.

The prime object of my present invention aims at the provision of an improved method for roasting sulphur bearing ores, such for example as iron and zinc sulphide, to produce therefrom an SO2 gas of high concentration and a metal oxide having a very low sulphur content which, if desired, may be granulated, sintered or nodulized in the process, the method being capable of being carried on in a continuous Way, with the 'roasting reactions under ready and facile control of the operator, the process being further capable of producing uniform resulting products and by uniform operation.

The successful roasting of sulphur bearing ores to accomplish the ends sought for ls beset with many difficulties. The strength of the resulting SO2 gas depends mainly upon the oxygen content used in the roasting process, the com- 5 bustion gases present (where carbon or hydrocarbons have been mixed with the ore) and the presence of contaminating gases such as sulphur trioxide (S03) which are incidentally and undesirably generated in the roasting operation. The character of the metal oxide produced depends upon the temperature, time, degree of oxidation and general control of the roasting reactions. Where oxygen of higher concentration than that contained in air was used in 1 prior processes, to produce S02 gas of increased strength, diflicultes arose due to the increased rate of combustion and high furnace temperatures. Where the rate of hflow of the air was sought to be controllably reduced to obtain the high strength of SOz,'the regulation of the temperatures in the .furnace nevertheless proved dif'cult and so far as I am aware, it was not feasible or possible to obtain an SO2 gas free from contamination with S03 or to obtain a 25 sufficiently desulphurized metal oxide-or one which was properly granulated as distinguished from being matted or coagulated. Where a diluent gas for the air or oxygen such as SO.` or CO2 was suggested, for the purpose of checking 30 the rate of combustion in the roasting furnace, or where this was combined with an attempted regulation of the oxygen content, it was still difflcult to prevent the formation of the trioxide of sulphur or to effect that completion of the oxidation desired to produce a properly granulated and desulphurized metal oxide. Where the process was carried out in a rotary kiln, various means had to be adopted in an endeavor to regulate the course of the roasting reaction; these 40 prove, however, difficult of accomplishment and do not anyway yield the desired results.

By the practice of the process of my present invention, I am enabled (1) to produce SO2 gas of high concentration substantially free of SO: gas, (2) to produce an oxide of the metal having a very low sulphur content such for example as 1% and even as low as 0.1%, (3) to produce a metal oxide which is granulated. or sintered in the process which may, without further processing, be used in the blast furnaces, (4) to carry out the process in a continuous operation in a rotary kiln, (5) to produce uniformity in resulting products, (6) to provide for easy and convenient control of the factors of reaction such as the time and temperature of reaction and the flow or movement of the reacting constituents,V

(7) to effectively dispose of the dust formed in the process whereby the SO: gas obtained is substantially'free from dust contamination and (8) to provide a method readily adaptable to the treatment of ores of different metals and different ores of the same metal.

To the accomplishment of the foregoing and such other objects as will hereinafter appear, my invention consists in the method and the steps of the method as hereinafter more particularly described and sought to be deiinedin the claims; reference being had to the accompanying drawing, which shows an apparatus preferably used in the practice of the method, and in which:

'Ihe figure is a diagrammatic view of a rotary kiln or furnace and associated equipment.

I have found that the objects of my present invention may be successfully achieved by properly governing both the magnitude or degree of the temperatures developed in the roasting operation and the distribution or zoning of the temperatures along the length of the roasting furnace. This I accomplish by controlling the flow of air "and the ow of ore through the furnace, which latter is preferably a rotary kiln, the control being such as to produce a roasting atmosphere in the kiln having a preferably continuously increasing temperature gradient which increases in the direction of the ore flow, and being further such that there takes place in the lower temperature stage of the roasting operation an -oxidation of the ore in an atmosphere critically low in free oxygen and in the higher temperature stage of the roasting operation a completion of the oxidation of the ore in an atmosphere having a substantial amount of free oxygen. By thus controlling the air flow an SO2 gas of high concentration is produced. By carrying out the first stage of the roasting operation in an atmosphere low in free oxygen andA the second stage in an atmosphere having a substantial amount of free oxygen, the formation 'of SO: is avoided or prevented because of the lack of available oxygen in the first stage, even though the temperatures therein are within the range of` catalytic or SO: formation temperatures, and because the temperatures in the second stage are above such catalytic temperatures, even though there is an available supply of free oxygen in this second stage. In the present embodiment of the invention, the degree and distribution of the furnace temperatures are further contr'olled by re-circulating in a predetermined section of the kiln a part of the sulphur dioxide produced in the process. The high degree of desulphurization and the obtaining of a granulated and sintered product thereby results. In the process the rate of roasting reaction and the temperature distribution are also controlled by the depth of the ore bed in the kiln and the rate of flow of the ore through the kiln. The kiln is operated with only one point of supply for the ore and one point of admission for the oxygen, these being admitted at opposite ends of the kiln and circulated through the kiln in countercurrent directions, and also with only one point of admission for the returned SO2 gas. There results a. simple control and operation and a thorough treatment of the ore.

Referring now to the drawing, the roasting operation is preferably practiced in a rotary kiln A into one end of which the ore or admixture is charged by means of a screw conveyor III, and

from the other end of which the solid residue of the treatment (the oxide of the metal) is discharged through a hopper I I. designed to carry a substantially deep bed of the ore O under treatment. The roasting operation is subdivided into a plurality of stages forming in sequence one continuousoperation; and this subdivision may, I have found. be efficiently accomplished by subdividing the rotary kiln into a number of compartments by means of annular partitions I2, l2, three or four compartments being preferred.

The SO2 gas produced in the process having a strength of about 12% (when treating pyrites or zinc concentrates) flows from the kiln through an exit flue Il, the separator I4, the cooler I4', and into a pipe I5 and thence directly to the condenser apparatus of a sulphuric acid producing system (when it is desired to produce sulphuric acid) such as set forth in my copending applications SerialNo. 575,549, filed November 17, 1931, or Serial No. 619.054flled June 24, 1932. The ore O continuously feeds through the kiln, the iron oxide product is continuously discharged therefrom, and the SO2 gas is continuously withdrawn from the kiln. Any dust formed in the process is separated by the air currents produced in the separator I4 and is deposited into the ore feed screw conveyor III and returned to the kiln with the ore.

The granulated metal oxide discharging from the hopper II feeds onto a conveyor I6 and into a storage hopper I1. The sulphide ore to be treated may be contained in the hopper I8 and feeds therefrom into the screw conveyor I0. The air supply is admitted to the metal oxide discharge end of the kiln through a conduit I9, the flow being controlled by a damper 20 therein, the air flowing through all of the kiln compartments counter-current to the ore flow therein. If desired, the air conduit may be associated with a fuel inlet (not shown) which may be used in starting up the furnace and which may also be used for other purposes, as hereinafter described.

To control the degree and distribution of the furnace temperatures, some of the SO2 gas produced in the process is returned to the kiln and is recirculated in a predetermined section thereof, the point of admission of the returned sulphur dioxide being selected so as to subdivide the kiln generally into the two roasting stages described, the first stage having a depleting or depleted oxygen supply and the second stage having an oxygen content of a substantial amount, the first stage being the lower temperature stage and the second the higher temperature stage. This is accomplished by providing an SO2 return line 2l connected by means of a pipe 22 to the SO2 efliux pipe I5, provided with a blower 23, the SO2 return line having a section 24 extending part way in the kiln and opening into an intermediate point thereof, as for example in the compartment b thereof. This SO2 line may also be provided with a controlling damper 25. By means of this arrangement, an excess of oxygen may be supplied to the end compartment c, and thus at the metal oxide discharge end of the kiln to secure the maximum temperatures in and around the adjoining parts of compartments b and c (and the maximum elimination of sulphur and proper nodulization of the discharging oxide ore), while the remainder of compartment b as well as the preheating compartment a are made to have an atmosphere containing a mixture of a depleted free oxygen content and SO: gas securing in these 'I'he rotary kiln is chambers a and b the desired control of the temperatures and the reduction of the oxygen content below the critical catalyzlng amount,

The reactions takinaplace in the kiln require a substantial amount of time for completion, and it is therefore desirable to maintain a substantially deep bed of the roasting mixture in the kiln, this being controlled by the height of the partition walls l2 and the end walls of the kiln, as well as by the speed of movement of the ore through the kiln. The mechanical condition of the metal oxide product is also controlled by the rate of feed of the ore, as well as by the kiln temperatures. The heat regulates the sintering or nodulizing of the product, and this combined with the time of reaction regulates the degree of desulphurization taking place.

The following example of the use of the complete process will serve to illustrate the preferred manner of practicing the same. The fresh ore is continuously fed from the screw conveyor I into the chamber a of the kiln. The kiln used may be 12 feet in length by 3 feet in diameter. The air flow into thev kiln is controlled so that the free or excess oxygen content of the produced SO: gases does not exceed and may be from 1 to 5% (being most generally around 2 to 3%). 'Ihe exit temperatures of the SO2 gases may be from 500 to 800 F. where sulphur dioxide is recirculated through the kiln as shown. These end temperatures may be lower where part of the produced metal oxide is vre circulated through the kiln, as described in my companion application filed concurrently herewith, Serial No. 636,141. The sintering or nodulizing of the ore may be carried out to any desired extent. The kiln compartments are provided with flights (not shown) which function to elevate the ore in the rotation of the kiln, thereby effecting a continued breaking up of the ore and preventing caking or matting of the product, the use of which flights also increasing the capacity of the roasting process. Preferably no flights are provided in the ore feed chamber a of the kiln; by not equipping the flights in this chamber a, the said chamber is made to act incidentally as a dust settling chamber, which chamber also fimctions mainly as a preheating chamber. Where four compartments are provided, the end compartment c need not be equipped with flights, since it is found that the absence thereof assists to some extent in nodulizing the product.

The process is controlled so as to make about the middle region of the end chamber c of the kiln the hottest end of the kiln, whereby a continuously increasing temperature gradient increasing in the direction of the ore flow is produced. This temperature gradient may range, in the embodiment herein described, from 500 F. in the chamber a to 1400 to 2000 F. in the chamber c. The air as it moves through the kiln becomes gradually depleted in available free oxygen, the chamber c having a substantial supply thereof whereas the chamber a has a critically low amount thereof. This air control combined with the admission of the SO2 gas to an intermediate point of the kiln and the controlled flow thereof yields an atmosphere in chambers a and b which, because of the depleting oxygen content, is not conducive to catalytic conversion of SO: to S03 or S03 formation in spite of the favorable catalytic temperatures therein, and yields temperatures in the region of chamber c adjoining chamber b which are above the catalytic or S0: formation temperatures, although the amount of oxygen therein would otherwise be favorable to SO; formation. vIn the' exit region of chamber c there is a drop in temperature; but here due to the absence of sulphur. there will be no formation of SO: regardless of the high oxygen content or temperature. Where four instead of three compartments are provided, the kiln is so subdivided that the hottest region of the kiln may be in the second compartment from the residue exit end of the kiln and thus in the compartment corresponding to compartment b. In such case the temperature gradient progressively increases over the length of three compartments. The sulphide ores used may contain from 35 to 45% sulphur, and. it is found that the desulphurization may be carried on to such an extent that the metal oxide product produced has a sulphur content as low as 0.1%.

To reduce any sulphates which may be contained in the ore, and also to obtain a hard sintered product whenever desired, a small proportion of powdered coke or coal, such for example as one half to 1% by weight of the ore, may be added to the ore; and this may be fed into the hopper I8. Additional fuel such as gas, hydrocarbon, etc., may be admitted to chamber c whenever a hard sntered product is desired and may also be used to return to the discharge chamber c of the kiln the high temperature zone when it tends to move to the middle chamber b. In the absence of the employment of either additional carbon or additional fuel, the carbon dioxide content of the produced gases is nil; and whenever some additional fuel is employed, the CO2 content is negligible. The sulphur dioxide which is returned to the kiln for re-circulation therein is cooled in transit and also by the cooler I4.

The manner of practicing the improved process of my presentinvention and the many advantages thereof will in the rrtain be fully apparent from the above detailed description thereof. The production of the SC3-free SO2 gas of high concentration and the metal oxide of very low sulphur content, as well as the Aobtaining of the other advantages set forth, results from the described governing or control of both the magnitude or degree of the temperatures developed in the roasting operation and the distribution or zoning of these temperatures along the length of the roasting furnace. e low temperatures at the gas exit end of the kiln not only favor the avoidance of S03 generation, but result in a low exit temperature for the SO2 gases. If any S03 is generated at the high temperature zone of the kiln, it is reduced in its transit through the lower temperature regions of the kiln so that the exit gases are free of S03 as described. The temperature control in and the practice of the process is such that the roasting may be and is carried on at the higher temperatures to effect substantially complete desulphurization of the ore with the obtaining of a granulated metal oxide and with the avoidance throughout the process of that matting, coagulationor fusion of the ore which characterizes prior roasting methods also aiming at substantially complete desulphurization of the ore. The high concentration, low temperature, SC3-free character and the low oxygen content of the SO2 gases produced are very important in enabling the produced gas to be utilized directly for making contact sulphuric acid without the expensive equipment for puriiication,` mist removal and treatment of large gas volumes used in prior contact plants; it being thus now made possible to' build a complete plant for making contact sulphuric acid at a cost very considerably lower than that heretofore possible with other methods.

While I have specified a range of temperatures within which it is possible to work the apparatus described, it will be understood that this range of temperatures may be widely varied, the temperature limits being inter-related with variations in ore composition, size or capacity of the plant, amount of recirculated ore or gas and the amount of free oxygen used. While I have mentioned the use of iron and zinc sulphide ores for the process, it will be understood that I am able to employ in the kiln all grades of ores from the low grade sulphur ysands to high grade concentrates, either iron, copper, lead or zinc. All of these 'can be used without the use of water cooled equipment and without caking or matting of the mass taking place. I have found that excellent eiilciency in complete extraction of the sulphur is had without the use of supplementary heat or carbonaceous material, these being employed only to assist in producing a hard sintered or nodulized product. In prior art roasting processes, external heat supplemental to that yielded by the sulphur content of the ore is used; and this supplemental heat is usually obtained by the carbon or hydrocarbons added to the ore. The present process may .be and is preferably practiced as stated without the use of supplementary heat or carbonaceous material, even though the resultant ore treated in the kiln has a relatively low sulphur content, the manner of carrying out the process together with the low temperatures employed over a region of the kiln, the high concentration of the gases obtained and the insulation provided for the kiln being factors in effecting and permitting that heat conservation which permits the practice of the process without the additional fuel. The granulated product of the kiln discharges therefrom in a continuous and easy flowing stream.

While I have described the process and apparatus to be used therefor showing the practice of the steps in the preferred manner, it will be apparent that I may make many changes and modifications therein without departing from the spirit of the invention, defined in the following claims.

I claim:

1. The process of treating sulphur bearing ores to desulphurize the same and to produce therefrom sulphur dioxide gas and a metal oxide, which consists in crculating the ore in a continuous roasting operation through a roasting atmosphere, in re-circulating at least a part of the produced sulphur dioxide through the roasting atmosphere, in fiowing oxygen through the roasting atmosphere, and in controlling the flow of the ore, the sulphur dioxide and the oxygen whereby there takes place in a low temperature stage of the roasting operation an oxidation of the ore in an atmosphere low in free oxygen and in a high temperature stage of the roasting operation a completion of the oxidation of the ore in an atmosphere having a substantial amount of free oxygen, the sulphur dioxide being introduced into the low temperature stage of the operation at a point beyond the high temperature stage without admixture with additional oxygen.

2. The process of treating sulphur bearing ores to desulphurize the same and to produce therefrom sulphur dioxide gas and a metal oxide, which consists in slowly circulating the ore inV a continuous roasting operation through a roasting atmosphere having a temperature gradient which increases in the direction of the ore now, in recirculating at least a part of the produced sulphur dioxide through the roasting atmosphere countercurrent to the ore flow, in flowing oxygen through the roasting atmosphere countercurrent `to the ore flow, and in controlling the flow of the ore, the sulphur dioxide and the oxygen whereby there takes place in a low temperature stage of the roasting operation an oxidation of the ore in an atmosphere low in i'ree oxygen and in a high temperature stage of the roasting operation a completion of the oxidation of the ore in an atmosphere having a substantial amount of free oxygen, the sulphur dioxide being introduced into the low temperature stage of the operation at a point beyond the high temperature stage without admixture with additional oxygen` 3. The process of treating sulphur bearing ores to desulphurize the same and to produce therefrom sulphur dioxide gas substantially free of SO: and a sintered metal oxide, which consists in slowly circulating the ore in a continuous roasting operation through a roasting atmosphere having a continuously increasing temperature gradient which increases in the direction of the ore ilow, in re-circulating at least a part of the produced sulphur dioxide through the roasting atmosphere, in ilowing oxygen through the roasting atmosphere, and in controlling the flow of the ore, the sulphur dioxide and the oxygen whereby there takes place in the low temperature stage of the roasting operation an oxidation of the ore in an atmosphere low in free oxygen and in the high temperature stage of the roasting operation a completion of the oxidation of the ore in an atmosphere having a substantial amount of free oxygen, the completion of the oxidation being carried out to produce a sintering or nodulizing of the metal oxide, the sulphur dioxide being introduced into the low temperature stage of the operation at a point beyond the high temperature stage Without admixture with additional oxygen.

4. 'I'he process of treating sulphur bearing ores to desulphurize the same and to produce therefrom sulphur dioxide gas and a metal oxide, which consists in slowly flowing the ore through a rotary kiln in a continuous roasting operation, the roasting atmosphere of the kiln having a temperature gradient which increases in the direction of the ore flow, in re-circulating at least a part of the produced sulphur dioxide through the kiln, in fiowlng oxygen through the kiln, and in controlling the ilow of ore, sulphur dioxide and oxygen whereby there takes place in the roasting stage at or below catalytic or S03 formation temperatures an oxidation of the ore in an atmosphere low in free oxygen and in the roasting stage above such temperatures a completion of the oxidation of the ore in an atmosphere having a substantial amount of free oxygen, the sulphur dioxide being introduced into the low temperature stage of the operation at a point beyond the high temperature stage without admixture with additional oxygen.

5. The process of treating sulphur bearing ores to desulphurize the same and to produce therefrom sulphur dioxide gas and a metal oxide, which consists in slowly fiowing a substantially deep bed of the ore through a rotary kiln in a continuous roasting operation, the roasting atmosphere of the kiln having a continuously increasing. temperature gradient' which increases in the direction of the ore ow, in re-trculating at least a, part of the produced sulphur dioxide through the kiln countercurrent to the ore flow, in owing oxygen through the kiln countercurrent to the ore 110W,

and in controlling the flow of ore, the sulphur dioxide and the oxygen whereby there takes place in a, low temperature stage of the roasting operation a slow oxidation of the ore in an atmos- 

